Cleaning compositions

ABSTRACT

This disclosure relates to a cleaning composition that contains 1) hydroxylamine, 2) an amino alcohol, 3) hexylene glycol, and 4) water.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.16/923,535, filed on Jul. 8, 2020, which is a continuation of U.S.application Ser. No. 16/278,875, filed on Feb. 19, 2019, now U.S. Pat.No. 10,752,867, which claims priority to U.S. Provisional ApplicationSer. No. 62/649,029, filed on Mar. 28, 2018. The contents of the priorapplications are hereby incorporated by reference in their entirety.

TECHNICAL FIELD

The present disclosure relates to novel cleaning compositions forsemiconductor substrates and methods of cleaning semiconductorsubstrates. More particularly, the present disclosure relates tocleaning compositions for semiconductor substrates after plasma etchingof metal layers or dielectric material layers deposited on thesubstrates and the removal of residues left on the substrates after bulkresist removal via a plasma ashing process.

BACKGROUND

In the manufacture of integrated circuit devices, photoresists are usedas an intermediate mask for transferring the original mask pattern of areticle onto the wafer substrate by means of a series ofphotolithography and plasma etching steps. One of the essential steps inthe integrated circuit device manufacturing process is the removal ofthe patterned photoresist films from the wafer substrate. In general,this step is carried out by one of two methods.

One method involves a wet stripping step in which thephotoresist-covered substrate is brought into contact with a photoresiststripper solution that consists primarily of an organic solvent and anamine. However, such stripper solutions generally cannot completely andreliably remove the photoresist films, especially if the photoresistfilms have been exposed to UV radiation and plasma treatments duringfabrication. Some photoresist films become highly crosslinked by suchtreatments and are more difficult to dissolve in a stripper solution. Inaddition, the chemicals used in these conventional wet-stripping methodsare sometimes ineffective for removing inorganic or organometallicresidual materials formed during the plasma etching of metal or oxidelayers with halogen-containing gases.

An alternative method of removing a photoresist film involves exposing aphotoresist-coated wafer to oxygen-based plasma in order to burn theresist film from the substrate in a process known as plasma ashing.However, plasma ashing is also not fully effective in removing theplasma etching by-products noted above. Instead, removal of these plasmaetch by-products is typically accomplished by subsequently exposing theprocessed metal and dielectric thin films to certain cleaning solutions.

Metal-containing substrates are generally susceptible to corrosion. Forexample, substrates such as aluminum, copper, aluminum-copper alloy,tungsten nitride, tungsten, cobalt, titanium oxide, other metals andmetal nitrides, will readily corrode. Further, dielectrics (e.g.,interlayer dielectrics or ultra low-k dielectrics) in the integratedcircuit devices can be etched by using conventional cleaningchemistries. In addition, the amount of corrosion tolerated by theintegrated circuit device manufacturers is getting smaller and smalleras the device geometries shrink.

At the same time, as residues become harder to remove and corrosion mustbe controlled to ever lower levels, cleaning solutions should be safe touse and environmentally friendly.

Therefore, the cleaning solutions should be effective for removing theplasma etch and plasma ashing residues and should also be non-corrosiveto all exposed substrate materials.

SUMMARY

The present disclosure is directed to non-corrosive cleaningcompositions that are useful for removing residues (e.g., plasma etchand/or plasma ashing residues) from a semiconductor substrate as anintermediate step in a multistep manufacturing process. These residuesinclude a range of relatively insoluble mixtures of organic compoundssuch as residual photoresist; organometallic compounds; metal oxidessuch as aluminum oxides (AlOx), titanium oxides (TiOx), zirconium oxides(ZrOx), tantalum oxides (TaOx), and hafnium oxides (HfOx) (which can beformed as reaction by-products from exposed metals); metals such asaluminum (Al), aluminum/copper alloy, copper (Cu), titanium (Ti),tantalum (Ta), tungsten (W), and cobalt (Co); metal nitrides such asaluminum nitrides (AlN), aluminum oxide nitrides (AlOxNy), titaniumnitrides (TiN), tantalum nitrides (TaN), and tungsten nitrides (WN);their alloys; and other materials. An advantage of the cleaningcomposition described herein is that it can clean a broad range ofresidues encountered and be generally non-corrosive to exposed substratematerials (e.g., exposed metal oxides (such as AlOx), metals (such asaluminum, aluminum/copper alloy, copper, titanium, tantalum, tungsten,and cobalt), metal nitrides (such as titanium, tantalum, and tungstennitrides), and their alloys).

In one aspect, the present disclosure features a cleaning compositioncomprising (e.g., consisting of or consisting essentially of): 1) atleast one redox agent; 2) at least one alkylsulfonic acid or a saltthereof, the alkylsulfonic acid comprising an alkyl group substituted byOH or NH₂; 3) at least one aminoalcohol; 4) at least one corrosioninhibitor; 5) at least one organic solvent; 6) water; and 7) optionally,at least one pH adjusting agent.

In another aspect, the present disclosure features a cleaningcomposition comprising (e.g., consisting of or consisting essentiallyof): 1) at least one redox agent; 2) at least one aminoalcohol; 3) atleast one corrosion inhibitor; 4) at least one organic solvent; 5)water; and 6) optionally, at least one pH adjusting agent.

In another aspect, the present disclosure features a method of cleaningresidues from a semiconductor substrate. The method includes contactinga semiconductor substrate containing post etch residues and/or post ashresidues with a cleaning composition described herein. For example, themethod can include the steps of: (A) providing a semiconductor substratecontaining post etch and/or post ash residues; (B) contacting saidsemiconductor substrate with a cleaning composition described herein;(C) rinsing said semiconductor substrate with a suitable rinse solvent;and (D) optionally, drying said semiconductor substrate by any meansthat removes the rinse solvent and does not compromise the integrity ofsaid semiconductor substrate.

The details of one or more embodiments of the invention are set forth inthe description below. Other features, objects, and advantages of theinvention will be apparent from the description and the claims.

DETAILED DESCRIPTION

As defined herein, unless otherwise noted, all percentages expressedshould be understood to be percentages by weight to the total weight ofthe cleaning composition. Unless otherwise noted, ambient temperature isdefined to be between about 16 and about 27 degrees Celsius (° C.), suchas 25° C.

As used herein, the terms “layer” and “film” are used interchangeably.

As defined herein, a “water-soluble” substance (e.g., a water-solublealcohol, ketone, ester, or ether) refers to a substance having asolubility of at least 0.1% by weight in water at 25° C.

In general, the present disclosure is directed to a cleaning composition(e.g., a non-corrosive cleaning composition) including: 1) at least oneredox agent; 2) at least one alkylsulfonic acid or a salt thereof, thealkylsulfonic acid comprising an alkyl group substituted by OH or NH₂;3) at least one aminoalcohol; 4) at least one corrosion inhibitor; 5) atleast one organic solvent (e.g., at least one water soluble organicsolvent selected from the group consisting of water soluble alcohols,water soluble ketones, water soluble esters, and water soluble ethers);6) water; and 7) optionally, at least one pH adjusting agent.

In some embodiments, the compositions of this disclosure contain atleast one (e.g., two, three, or four) redox agent, which is believed toaid in the dissolution of residues on the semiconductor surface such asphotoresist residues, metal residues, and metal oxide residues. As usedherein, the term “redox agent” refers to a compound that can induce anoxidation and/or a reduction in a semiconductor cleaning process. Anexample of a suitable redox agent is hydroxylamine. In some embodiments,the redox agent or the cleaning composition described herein does notinclude a peroxide (e.g., hydrogen peroxide).

In some embodiments, the at least one redox agent can be at least about6% by weight (e.g., at least about 7% by weight, at least about 8% byweight, at least about 9% by weight, at least about 10% by weight, atleast about 11% by weight, or at least about 12% by weight) and/or atmost about 15% by weight (e.g., at most about 14% by weight, at mostabout 13% by weight, at most about 12% by weight, at most about 11% byweight, or at most about 10% by weight) of the cleaning compositions ofthis disclosure.

In some embodiments, the cleaning compositions of this disclosureinclude the at least one (e.g., two, three, or four) alkylsulfonic acidor a salt thereof, the alkylsulfonic acid containing an alkyl groupsubstituted by OH or NH₂. In some embodiments, the at least onealkylsulfonic acid includes an alkylsulfonic acid of formula (I):R—SO₃H  (I),in which R is C₁-C₁₀ alkyl substituted by at least one substituentselected from the group consisting of OH and NH₂. In some embodiment, Ris C₁-C₄ alkyl substituted by at least one OH. For example, the at leastone alkylsulfonic acid or a salt thereof (e.g., a salt free of metalions such as alkali metal ions) can include HO(CH₂)₂SO₃H orHO(CH₂)₂SO₃NH₄. In some embodiments, the cleaning compositions of thisdisclosure do not contain the above alkylsulfonic acid or a salt thereof(e.g., an salt containing a metal ion such as an alkali metal ion).

In some embodiments, the at least one alkylsulfonic acid or a saltthereof can be at least about 0.3% by weight (e.g., at least about 0.4%by weight, at least about 0.5% by weight, at least about 0.6% by weight,at least about 0.7% by weight, at least about 0.8% by weight, at leastabout 0.9% by weight, at least about 1% by weight, at least about 1.5%by weight, or at least about 2% by weight) and/or at most about 5% byweight (e.g., at most about 4% by weight, at most about 3% by weight, atmost about 2% by weight, at most about 1.5% by weight, at most about1.2% by weight, or at most about 1% by weight) of the cleaningcompositions of this disclosure. Without wishing to be bound by theory,it is believed that a cleaning composition including the alkylsulfonicacid or a salt thereof in the amount specified above can reduce thecorrosion effects of the composition on certain exposed substratematerials (e.g., AlOx) that are not intended to be removed during thecleaning process (e.g., by lowering the etch rates of the cleaningcomposition on such exposed substrate materials).

In some embodiments, the cleaning compositions of this disclosurecontain at least one (e.g., two, three, or four) aminoalcohol. As usedherein, the term “aminoalcohol” refers to a compound that include atleast one (e.g., two, three, or four) amino group and at least one(e.g., two, three, or four) hydroxyl group. In some embodiments, theaminoalcohol can be a compound of formula (I): H₂N—R—OH (I), in which Ris C₁-C₆ straight or branched alkylene or oxyalkylene. Examples ofsuitable aminoalcohols include ethanolamine and2-(2-aminoethoxy)ethanol.

In some embodiments, the at least one aminoalcohol can be at least about5% by weight (e.g., at least about 5.5% by weight, at least about 6% byweight, at least about 6.5% by weight, at least about 7% by weight, orat least about 7.5% by weight) and/or at most about 10% by weight (e.g.,at most about 9.5% by weight, at most about 9% by weight, at most about8.5% by weight, or at most about 8% by weight) of the cleaningcompositions of this disclosure. Without wishing to be bound by theory,it is believed that the aminoalcohols can aid in the dissolution ofresidues on the semiconductor surface (such as photoresist residues,metal residues, and metal oxide residues) by, for example, serving as anoxidizing agent, hydrogen bonding with hydroxylamine to make it moreeffective in the cleaning compositions, swelling/dissolving the etchresidue, or a combination of the above mechanisms.

In some embodiments, the cleaning compositions of this disclosurecontain at least one (e.g., two, three, or four) corrosion inhibitor. Insome embodiments, the corrosion inhibitors can be selected fromsubstituted or unsubstituted benzotriazoles. Without wishing to be boundby theory, it is believed that such cleaning compositions can exhibitsignificantly improved compatibility with materials (e.g., AlOx or Co)that may be present in the semiconductor substrate and should not beremoved by the cleaning compositions, when compared to cleaningcompositions without any corrosion inhibitor.

Suitable classes of substituted benzotriazole include, but are notlimited to, benzotriazoles substituted by at least one substituentselected from the group consisting of alkyl groups, aryl groups, halogengroups, amino groups, nitro groups, alkoxy groups, and hydroxyl groups.Substituted benzotriazoles also include those fused with one or morearyl (e.g., phenyl) or heteroaryl groups.

Suitable examples of a corrosion inhibitor include, but are not limitedto, benzotriazole (BTA), 5-aminotetrazole, 1-hydroxybenzotriazole,5-phenylthiol-benzotriazole, 5-chlorobenzotriazole,4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole,5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole,tolyltriazole, 5-phenyl-benzotriazole, 5-n itrobenzotriazole, 4-nitrobenzotriazole, 3-amino-5-mercapto-1,2,4-triazole,2-(5-amino-pentyl)-benzotriazole, 1-amino-benzotriazole,5-methylbenzotriazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole,4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole,5-isopropylbenzotriazole, 4-n-butylbenzotriazole,5-n-butylbenzotriazole, 4-isobutylbenzotriazole,5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole,4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-m ethoxybenzotriazole,5-hydroxybenzotriazole, dihydroxypropylbenzotriazole,1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-t-butylbenzotriazole, 5-(1′,1′-dimethylpropyl)-benzotriazole,5-(1′,1′,3′-trimethylbutyl)benzotriazole, 5-n-octyl benzotriazole, and5-(1′,1′,3′,3′-tetramethylbutyl)benzotriazole.

In some embodiments, the at least one corrosion inhibitor can be atleast about 0.1% by weight (e.g., at least about 0.2% by weight, atleast about 0.3% by weight, at least about 0.4% by weight, or at leastabout 0.5% by weight) and/or at most about 2% by weight (e.g., at mostabout 1.8% by weight, at most about 1.6% by weight, at most about 1.4%by weight, at most about 1.2% by weight, or at most about 1% by weight)of the cleaning compositions of this disclosure.

In some embodiments, the cleaning compositions of this disclosurecontain at least one (e.g., two, three, four, or more) organic solvent,e.g., at least one water soluble organic solvent selected from the groupconsisting of water soluble alcohols, water soluble ketones, watersoluble esters, and water soluble ethers (e.g., glycol diethers).

Classes of water soluble alcohols include, but are not limited to,alkane diols (including, but not limited to, alkylene glycols), glycols,alkoxyalcohols (including, but not limited to, glycol monoethers),saturated aliphatic monohydric alcohols, unsaturated non-aromaticmonohydric alcohols, and low molecular weight alcohols containing a ringstructure. Examples of water soluble alkane diols includes, but are notlimited to, 2-methyl-1,3-propanediol, 1,3-propanediol,2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol,1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycols. Examplesof water soluble alkylene glycols include, but are not limited to,ethylene glycol, propylene glycol, hexylene glycol, diethylene glycol,dipropylene glycol, triethylene glycol and tetraethylene glycol.

Examples of water soluble alkoxyalcohols include, but are not limitedto, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol,1-methoxy-2-butanol, and water soluble glycol monoethers. Examples ofwater soluble glycol monoethers include, but are not limited to,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,ethylene glycol mono n-propyl ether, ethylene glycol monoisopropylether, ethylene glycol mono n-butyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, diethylene glycolmonobutylether, triethylene glycol monomethyl ether, triethylene glycolmonoethyl ether, triethylene glycol monobutyl ether,1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol,2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropyleneglycol monomethyl ether, dipropylene glycol monoethyl ether, dipropyleneglycol mono-n-propyl ether, tripropylene glycol monoethyl ether,tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether,and diethylene glycol monobenzyl ether.

Examples of water soluble saturated aliphatic monohydric alcoholsinclude, but are not limited to, methanol, ethanol, n-propyl alcohol,isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butylalcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol.

Examples of water soluble unsaturated non-aromatic monohydric alcoholsinclude, but are not limited to, allyl alcohol, propargyl alcohol,2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.

Examples of water soluble, low molecular weight alcohols containing aring structure include, but are not limited to, tetrahydrofurfurylalcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

Examples of water soluble ketones include, but are not limited to,acetone, cyclobutanone, cyclopentanone, diacetone alcohol, 2-butanone,2,5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone,1,3-cyclohexanedione, and cyclohexanone.

Examples of water soluble esters include, but are not limited to, ethylacetate, glycol monoesters such as ethylene glycol monoacetate anddiethylene glycol monoacetate, and glycol monoether monoesters such aspropylene glycol monomethyl ether acetate, ethylene glycol monomethylether acetate, propylene glycol monoethyl ether acetate, and ethyleneglycol monoethyl ether acetate.

In some embodiments, the at least one organic solvent can be at leastabout 30% by weight (e.g., at least about 35% by weight, at least about40% by weight, or at least about 45% by weight) and/or at most about 50%by weight (e.g., at most about 45% by weight, at most about 40% byweight, or at most about 30% by weight) of the cleaning compositions ofthis disclosure.

The cleaning compositions of the present disclosure further includewater. Preferably, the water is de-ionized and ultra-pure, contains noorganic contaminants and has a minimum resistivity of about 4 to about17 mega Ohms. More preferably, the resistivity of the water is at least17 mega Ohms.

In some embodiments, water can be at least about 20% by weight (e.g., atleast about 25% by weight, at least about 30% by weight, at least about35% by weight, or at least about 40% by weight) and/or at most about 50%by weight (e.g., at most about 45% by weight, at most about 40% byweight, at most about 35% by weight, or at most about 30% by weight) ofthe cleaning compositions of this disclosure.

In some embodiments, the cleaning compositions of this disclosure canoptionally contain at least one pH adjusting agent (e.g., an acid or abase) to control the pH to from about 8 to about 11. In someembodiments, the compositions of this disclosure can have a pH of atleast about 8 (e.g., at least about 8.5, at least about 9, at leastabout 9.5, or at least about 10) to at most about 11 (e.g., at mostabout 10.5, at most about 10, at most about 9.5, or at most about 9).Without wishing to be bound by theory, it is believed that a cleaningcomposition having a pH lower than 8 or higher than 11 would increasethe etch rate of certain metals or dielectric materials to anundesirable level. The effective pH can vary depending on the types andamounts of the ingredients used in the cleaning compositions describedherein.

The amount of the pH adjusting agent required, if any, can vary as theconcentrations of the other components (e.g., the hydroxylamine, thealkylsulfonic acid, the aminoalcohol, and the corrosion inhibitor) arevaried in different formulations, and as a function of the molecularweight of the particular pH adjusting agent employed. In general, the pHadjusting agent concentration ranges from about 1% to about 10% byweight of the cleaning composition. In some embodiments, the cleaningcompositions of this disclosure include at least about 1% by weight(e.g., at least about 1.5% by weight, at least about 2% by weight, or atleast about 2.5% by weight) and/or at most about 10% by weight (e.g., atmost about 9% by weight, at most about 8% by weight, at most about 7% byweight, at most about 6% by weight, or at most about 5% by weight) thepH adjusting agent.

In some embodiments, the pH adjusting agent is free of any metal ion(except for a trace amount of metal ion impurities). Suitable metal ionfree pH adjusting agents include acids and bases. Suitable acids thatcan be used as a pH adjusting agent include carboxylic acids andsulfonic acids. Exemplary carboxylic acid include, but are not limitedto, monocarboxylic acids, bicarboxylic acids, tricarboxylic acids,α-hydroxyacids and β-hydroxyacids of monocarboxylic acids,α-hydroxyacids or β-hydroxyacids of bicarboxylic acids, orα-hydroxyacids and β-hydroxyacids of tricarboxylic acids. In someembodiments, the at least one carboxylic acid includes citric acid,maleic acid, fumaric acid, lactic acid, glycolic acid, oxalic acid,tartaric acid, succinic acid, or benzoic acid. Examples of sulfonicacids of include, but are not limited to, methanesulfonic acid,trifluoromethanesulfonic acid, ethanesulfonic acid,trifluoroethanesulfonic acid, perfluoroethylsulfonic acid,perfluoro(ethoxyethane)sulfonic acid, perfluoro(methoxyethane)sulfonicacid, dodecylsulfonic acid, perfluorododecylsulfonic acid,butanesulfonic acid, perfluorobutanesulfonic acid, propanesulfonic acid,perfluoropropanesulfonic acid, octylsulfonic acid,pefluorooctanesulfonic acid, methanedisulfonic acid,2-methylpropanesulfonic acid, cyclohexylsulfonic acid, camphorsulfonicacids, perfluorohexanesulfonic acid, ethanedisulfonic acid,benzylsulfonic acid, hydroxyphenylmethanesulfonic acid,naphthylmethanesulfonic acid, norbornanesulfonic acids. benzenesulfonicacid, chlorobenzenesulfonic acids, bromobenzenesulfonic acids,fluorobenzenesulfonic acids, hydroxybenzenesulfonic acids,nitrobenzenesulfonic acids, 2-hydroxy-5-sulfobenzoic acid,benzenedisulfonic acids, toluenesulfonic acids (e.g., p-toluenesulfonicacid), methylchlorobenzenesulfonic acids, dodecylbenzenesulfonic acids,butylbenzenesulfonic acids, cyclohexylbenzenesulfonic acids,picrylsulfonic acid, dichlorobenzenesulfonic acids,dibromobenzenesulfonic acids, and 2,4,5-trichlorobenzenesulfonic acid.

Suitable bases that can be used as a pH adjusting agent include ammoniumhydroxide, quaternary ammonium hydroxides, monoamines (includingalkanolamines), imines (such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU)and 1,5-diazabicyclo[4.3.0]-5-nonene), and guanidine salts (such asguanidine carbonate). Examples of suitable quaternary ammoniumhydroxides include, but are not limited to, tetramethyl ammoniumhydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammoniumhydroxide, tetrabutyl ammonium hydroxide, dimethyldiethylammoniumhydroxide, choline, tetraethanolammonium hydroxide,benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, andbenzyltributylammonium hydroxide. Examples of suitable monoaminesinclude, but are not limited to, triethylamine, tributylamine,tripentylamine, ethanolamine, diethanolamine, diethylamine, butylamine,dibutylamine, and benzylamine.

In addition, in some embodiments, the cleaning compositions of thepresent disclosure may contain additives such as, additional pHadjusting agents, additional corrosion inhibitors, additional organicsolvents, surfactants, biocides, and defoaming agents as optionalcomponents. Examples of suitable defoaming agents include polysiloxanedefoamers (e.g., polydimethylsiloxane), polyethylene glycol methyl etherpolymers, ethylene oxide/propylene oxide copolymers, and glycidyl ethercapped acetylenic diol ethoxylates (such as those described in U.S. Pat.No. 6,717,019, herein incorporated by reference).

In some embodiments, the cleaning compositions of the present disclosuremay specifically exclude one or more of the additive components, in anycombination, if more than one. Such components are selected from thegroup consisting of polymers, oxygen scavengers, quaternary ammoniumsalts including quaternary ammonium hydroxides, amines, alkaline bases(such as NaOH, KOH, LiOH, Mg(OH)₂, and Ca(OH)₂), surfactants other thana defoamer, a defoamer, fluoride-containing compounds, oxidizing agents(e.g., peroxides, hydrogen peroxide, ferric nitrate, potassium iodate,potassium permanganate, nitric acid, ammonium chlorite, ammoniumchlorate, ammonium iodate, ammonium perborate, ammonium perchlorate,ammonium periodate, ammonium persulfate, tetramethylammonium chlorite,tetramethylammonium chlorate, tetramethylammonium iodate,tetramethylammonium perborate, tetramethylammonium perchlorate,tetramethylammonium periodate, tetramethylammonium persulfate, ureahydrogen peroxide, and peracetic acid), abrasives, silicates,hydroxycarboxylic acids, carboxylic and polycarboxylic acids (e.g.,those lacking amino groups), silanes (e.g., alkoxysilanes), cycliccompounds (e.g., cyclic compounds containing at least two rings, such assubstituted or unsubstituted naphthalenes, or substituted orunsubstituted biphenylethers), chelating agents, non-azole corrosioninhibitors, buffering agents, guanidine, guanidine salts, acids such asorganic acids and inorganic acids (e.g., sulfonic acids, sulfuric acid,sulfurous acid, nitrous acid, nitric acid, phosphorous acid, andphosphoric acid), pyrrolidone, polyvinyl pyrrolidone, metal salts (e.g.,metal halides such as metal halides of the formula W_(z)MX_(y), whereinW is selected from H, an alkali or alkaline earth metal, and ametal-ion-free hydroxide base moiety; M is a metal selected from thegroup consisting of Si, Ge, Sn, Pt, P, B, Au, Ir, Os, Cr, Ti, Zr, Rh, Ruand Sb; y is from 4 to 6; and z is 1, 2, or 3), and corrosion inhibitorsother than those described in this disclosure.

The cleaning compositions described herein can be prepared by simplymixing the components together, or can be prepared by blending twocompositions in a kit.

In some embodiments, the cleaning compositions of the present disclosureare not specifically designed to remove bulk photoresist films fromsemiconductor substrates. Rather, the cleaning compositions of thepresent disclosure can be designed to remove all residues after bulkresist removal by dry or wet stripping methods. Therefore, in someembodiments, the cleaning method of the present disclosure is preferablyemployed after a dry or wet photoresist stripping process. Thisphotoresist stripping process is generally preceded by a patterntransfer process, such as an etch or implant process, or it is done tocorrect mask errors before pattern transfer. The chemical makeup of theresidue will depend on the process or processes preceding the cleaningstep.

Any suitable dry stripping process can be used to remove bulk resistfrom semiconductor substrates. Examples of suitable dry strippingprocesses include oxygen based plasma ashing, such as a fluorine/oxygenplasma or a N₂/H₂ plasma; ozone gas phase-treatment; fluorine plasmatreatment, hot H₂ gas treatment (such as that described in U.S. Pat. No.5,691,117 incorporated herein by reference in its entirety), and thelike. In addition, any conventional organic wet stripping solution knownto a person skilled in the art can be used to remove bulk resist fromsemiconductor substrates.

A preferred stripping process used in combination with the cleaningmethod of the present disclosure is a dry stripping process. Preferably,this dry stripping process is the oxygen based plasma ashing process.This process removes most of the photoresist from the semiconductorsubstrate by applying a reactive-oxygen atmosphere at elevatedtemperatures (typically 250° C.) at vacuum conditions (i.e., 1 torr).Organic materials are oxidized by this process and are removed with theprocess gas. However, this process generally does not remove allinorganic or organometallic contamination from the semiconductorsubstrate. A subsequent cleaning of the semiconductor substrate with thecleaning composition of the present disclosure is typically necessary toremove those residues.

In some embodiments, the present disclosure features methods of cleaningresidues from a semiconductor substrate. Such methods can be performed,for example, by contacting a semiconductor substrate containing postetch residues and/or post ash residues with a cleaning compositiondescribed herein. The method can further include rinsing thesemiconductor substrate with a rinse solvent after the contacting stepand/or drying the semiconductor substrate after the rinsing step. Insome embodiments, the semiconductor substrate can further include atleast one material (e.g., an exposed material) or a layer of the atleast one material, where the material is selected from the groupconsisting of Cu, Co, W, AlOx, AlN, AlOxNy, Ti, TiN, Ta, TaN, TiOx,ZrOx, HfOx, and TaOx.

In some embodiments, the cleaning method includes the steps of: (A)providing a semiconductor substrate containing post etch and/or post ashresidues; (B) contacting said semiconductor substrate with a cleaningcomposition described herein; (C) rinsing said semiconductor substratewith a suitable rinse solvent; and (D) optionally, drying saidsemiconductor substrate by any suitable means that removes the rinsesolvent and does not compromise the integrity of said semiconductorsubstrate. In some embodiments, the cleaning method further includesforming a semiconductor device (e.g., an integrated circuit device suchas a semiconductor chip) from the semiconductor substrate obtained bythe method described above.

In some embodiments, the cleaning method does not substantially removeCo, aluminum oxides (AlOx or Al₂O₃), silicon oxides (SiOx), zirconiumoxide (ZrOx), TiN, SiN, poly-Si, or Cu in the semiconductor substrate.For example, in some embodiments, the method removes no more than about5% by weight (e.g., no more than about 3% by weight, no more than about1% by weight, no more than about 0.5% by weight, or no more than about0.1% by weight) of any of the above materials in the semiconductorsubstrate.

The semiconductor substrates to be cleaned in this method can containorganic and organometallic residues, and additionally, a range of metaloxides that need to be removed. Semiconductor substrates typically areconstructed of silicon, silicon germanium, Group III-V compounds likeGaAs, or any combination thereof. The semiconductor substrates canadditionally contain exposed integrated circuit structures such asinterconnect features (e.g., metal lines and dielectric materials).Metals and metal alloys used for interconnect features include, but arenot limited to, aluminum, aluminum alloyed with copper, copper,titanium, tantalum, cobalt, and silicon, titanium nitride, tantalumnitride, tungsten, and their alloys. The semiconductor substrate canalso contain layers of interlayer dielectrics, silicon oxide, siliconnitride, silicon carbide, titanium oxide, and carbon doped siliconoxides.

The semiconductor substrate can be contacted with a cleaning compositionby any suitable method, such as placing the cleaning composition into atank and immersing and/or submerging the semiconductor substrates intothe cleaning composition, spraying the cleaning composition onto thesemiconductor substrate, streaming the cleaning composition onto thesemiconductor substrate, or any combinations thereof. Preferably, thesemiconductor substrates are immersed into the cleaning composition.

The cleaning compositions of the present disclosure may be effectivelyused up to a temperature of about 90° C. (e.g., from about 25° C. toabout 80° C., from about 30° C. to about 60° C., or from about 40° C. toabout 60° C.).

Similarly, cleaning times can vary over a wide range depending on theparticular cleaning method and temperature employed. When cleaning in animmersion batch type process, a suitable time range is, for example, upto about 60 minutes (e.g., from about 1 minute to about 60 minutes, fromabout 3 minutes to about 20 minutes, or from about 4 minutes to about 15minutes).

Cleaning times for a single wafer process may range from about 10seconds to about 5 minutes (e.g., from about 15 seconds to about 4minutes, from about 15 seconds to about 3 minutes, or from about 20seconds to about 2 minutes).

To further promote the cleaning ability of the cleaning composition ofthe present disclosure, mechanical agitation means can be employed.Examples of suitable agitation means include circulation of the cleaningcomposition over the substrate, streaming or spraying the cleaningcomposition over the substrate, and ultrasonic or megasonic agitationduring the cleaning process. The orientation of the semiconductorsubstrate relative to the ground may be at any angle. Horizontal orvertical orientations are preferred.

The cleaning compositions of the present disclosure can be used inconventional cleaning tools known to those skilled in the art. Asignificant advantage of the compositions of the present disclosure isthat they include relatively non-toxic, non-corrosive, and non-reactivecomponents in whole and in part, whereby the compositions are stable ina wide range of temperatures and process times. The compositions of thepresent disclosure are chemically compatible with practically allmaterials used to construct existing and proposed semiconductor wafercleaning process tools for batch and single wafer cleaning.

Subsequent to the cleaning, the semiconductor substrate can be rinsedwith a suitable rinse solvent for about 5 seconds up to about 5 minuteswith or without agitation means. Examples of suitable rinse solventsinclude, but are not limited to, deionized (DI) water, methanol,ethanol, isopropyl alcohol, N-methylpyrrolidinone, gamma-butyrolactone,dimethyl sulfoxide, ethyl lactate and propylene glycol monomethyl etheracetate. Alternatively, aqueous rinses with pH>8 (such as dilute aqueousammonium hydroxide) may be employed. Preferred examples of rinsesolvents include, but are not limited to, dilute aqueous ammoniumhydroxide, DI water, methanol, ethanol and isopropyl alcohol. Thesolvent may be applied using means similar to that used in applying acleaning composition described herein. The cleaning composition may havebeen removed from the semiconductor substrate prior to the start of therinsing step or it may still be in contact with the semiconductorsubstrate at the start of the rinsing step. Preferably, the temperatureemployed in the rinsing step is between 16° C. and 27° C.

Optionally, the semiconductor substrate is dried after the rinsing step.Any suitable drying means known in the art may be employed. Examples ofsuitable drying means include spin drying, flowing a dry gas across thesemiconductor substrate, or heating the semiconductor substrate with aheating means such as a hotplate or infrared lamp, Marangoni drying,Rotagoni drying, IPA drying or any combinations thereof. Drying timeswill be dependent on the specific method employed but are typically onthe order of 30 seconds up to several minutes.

In some embodiments, a method of manufacturing an integrated deviceusing a cleaning composition described herein can include the followingsteps. First, a layer of a photoresist is applied to a semiconductorsubstrate. The semiconductor substrate thus obtained can then undergo apattern transfer process, such as an etch or implant process, to form anintegrated circuit. The bulk of the photoresist can then be removed by adry or wet stripping method (e.g., an oxygen based plasma ashingprocess). Remaining residues on the semiconductor substrate can then beremoved using a cleaning composition described herein in the mannerdescribed above. The semiconductor substrate can subsequently beprocessed to form one or more additional circuits on the substrate orcan be processed to form into a semiconductor chip by, for example,assembling (e.g., dicing and bonding) and packaging (e.g., chipsealing).

The contents of all publications cited herein (e.g., patents, patentapplication publications, and articles) are hereby incorporated byreference in their entirety.

EXAMPLES

The present disclosure is illustrated in more detail with reference tothe following examples, which are for illustrative purposes and shouldnot be construed as limiting the scope of the present disclosure. Anypercentages listed are by weight (wt %) unless otherwise specified.Controlled stirring during testing was done with a 1 inch stirring barat 300 rpm unless otherwise noted.

General Procedure 1 Formulation Blending

Samples of cleaning compositions were prepared by adding, whilestirring, to the calculated amount of organic solvent the remainingcomponents of the formulation. After a uniform solution was achieved,optional additives, if used, were added.

General Procedure 2 Cleaning Evaluation with Beaker Test

The cleaning of PER (Post Etch Residue) from a substrate was carried outwith the described cleaning compositions using a multilayeredsemiconductor substrate of photoresist/TiOx/SiN/Co/ILD (ILD=Inter LayerDielectric) or photoresist/TiOx/SiN/W/ILD that had been patternedlithographically, etched in a plasma metal etcher, and followed byoxygen plasma ashing to remove the top layer of photoresist completely.

The test coupons were held using 4″ long plastic locking tweezers,whereby the coupon could then be suspended into a 500 ml volume beakercontaining approximately 200 milliliters of the cleaning compositions ofthe present disclosure. Prior to immersion of the coupon into thecleaning composition, the composition was pre-heated to the desired testcondition temperature (typically 40° C. or 70° C. as noted) withcontrolled stirring. The cleaning tests were then carried out by placingthe coupon which was held by the plastic tweezers into the heatedcomposition in such a way that the PER layer containing side of thecoupon faced the stir bar. The coupon was left static in the cleaningcomposition for a time period (typically 2 to 5 minutes) while thecomposition was kept at the test temperature under controlled stirring.When the desired cleaning time was completed, the coupon was quicklyremoved from the cleaning composition and placed in a 500 ml plasticbeaker filled with approximately 400 ml of DI water at ambienttemperature (˜17° C.) with gentle stirring. The coupon was left in thebeaker of DI water for approximately 15 seconds, and then quicklyremoved, followed by a rinse in isopropanol for about 30 seconds. Thecoupon was immediately exposed to a nitrogen gas stream from a hand heldnitrogen blowing gun, which caused any droplets on the coupon surface tobe blown off the coupon, and further, to completely dry the coupondevice surface. Following this final nitrogen drying step, the couponwas removed from the plastic tweezers holder and placed into a coveredplastic carrier with the device side up for short term storage. Thescanning electron microscopy (SEM) images were then collected for keyfeatures on the cleaned test coupon device surface.

General Procedure 3 Materials Compatibility Evaluation with Beaker Test

The blankets W on silicon substrate, TiOx on SiO₂ on silicon substrate,SiN on silicon substrate, Al₂O₃ on silicon substrate, TiN on siliconsubstrate, ILD on silicon substrate were diced into approximately 1inch×1 inch square test coupons for the materials compatibility tests.The test coupons were initially measured for thickness or sheetresistance by the 4-point probe, CDE Resmap 273 for metallic film (Co,W), or by Elipsometry for dielectric film (TiOx, SiN and ILD) using aWoollam M-2000X. The test coupons were then installed on the 4″ longplastic locking tweezers and treated as described in the cleaningprocedure in General Procedure 3 with the Co, W, TiOx, SiN, or ILD layercontaining side of the coupon faced the stir bar for 10 minutes.

After the final nitrogen drying step, the coupon was removed from theplastic tweezers holder and placed into a covered plastic carrier. Thepost-thickness or sheet resistance was then collected on thepost-processing test coupon surface by the 4-point probe, CDE Resmap 273for metallic film (Co and W) or by Elipsometry for dielectric film(TiOx, SiN and ILD) using a Woollam M-2000X.

Example 1

Formulation Examples 1-11 (FE-1 to FE-11) and Comparative FormulationExamples 1-16 (CFE-1 to CFE-16) were prepared according to GeneralProcedure 1, and evaluated according to General Procedures 2 and 3. Theformulations are summarized in Table 1 and the cleaning results and theetch rates (ER) (Angstroms/minute) of Co, W, AlOx, TiOx, and B-doped Ware summarized in Table 2. The results in Table 2 were obtained at acleaning temperature of 65° C. within a cleaning time of 3-6 minutes.

TABLE 1 pH Adjusting IA or DI Ex. HA PG MEA agent its salt 5MBTAAdditive Water Total PH FE-1 10.00% 44.35% 9.25% — IAAS 0.50% — 35.00%100.00% 10.6 0.90% FE-2 10.00% 48.60% 5.00% — IAAS 0.50% — 35.00%100.00% 10.3 0.90% FE-3 10.00% 41.35% 7.00% MSA IAAS 0.50% — 35.00%100.00% 9.3 5.25% 0.90% FE-4 10.00% 41.35% 7.00% MSA IA 0.50% — 35.00%100.00% 9.3 5.25% 0.90% FE-5 10.00% 44.10% 7.00% MSA IA 0.50% — 35.00%100.00% 10.5 2.50% 0.90% FE-6 8.00% 45.10% 8.00% MSA IA 0.50% — 35.00%100.00% 10.6 2.50% 0.90% FE-7 10.00% 41.75% 7.00% MSA IAAS 0.50% —35.00% 100.00% 9.3 5.25% 0.50% FE-8 10.00% 42.25% 7.00% MSA — 0.50% —35.00% 100.00% 9.3 5.25% FE-9 10.00% 41.77% 7.00% MSA IA 0.50% — 35.00%100.00% 9.3 5.43% 0.30% FE-10 10.00% 44.87% 7.00% HCI IAAS 0.50% —35.00% 100.00% 9.3 1.73% 0.90% FE-11 10.00% 36.35% 7.00% MSA IAAS 0.50%— 40.00% 100.00% 9.3 5.25% 0.90% CFE-1 4.00% 58.92% — DBU IAAS 0.50% —35.00% 100.00% 10.1 1.08% 0.50% CFE-2 6.00% 56.93% — DBU IAAS 0.50% —35.00% 100.00% 10.1 1.07% 0.50% CFE-3 8.00% 54.92% — DBU IAAS 0.50% —35.00% 100.00% 10.1 1.08% 0.50% CFE-4 4.00% 58.52% — DBU IAAS 0.50% —35.00% 100.00% 10.1 1.08% 0.90% CFE-5 6.00% 56.53% — DBU IAAS 0.50% —35.00% 100.00% 10.1 1.07% 0.90% CFE-6 8.00% 54.52% — DBU IAAS 0.50% —35.00% 100.00% 10.1 1.08% 0.90% CFE-7 10.00% 52.13% — DBU IAAS 0.50%(NH₄)₂TiF₆ 35.00% 100.00% 10.1 1.46% 0.90% 0.007% CFE-8 10.00% 52.87% —DBU IAAS 0.10% (NH₄)₂TiF₆ 35.00% 100.00% 10.1 1.12% 0.90% 0.007% CFE-910.00% 52.87% — DBU IAAS 0.10% (NH₄)₂TiF₆ 35.00% 100.00% 10.1 1.12%0.90% 0.014% CFE-10 10.00% 52.67% — DBU IAAS 0.30% (NH₄)₂TiF₆ 35.00%100.00% 10.1 1.12% 0.90% 0.014% CFE-11 10.00% 52.37% — DBU IAAS 0.30%(NH₄)₂TiF₆ 35.00% 100.00% 10.1 1.42% 0.90% 0.014% CFE-12 10.00% 31.59%18.50% MSA IAAS 0.50% — 35.00% 100.00% 10.2 3.51% 0.90% CFE-13 10.00%51.10% 2.50% — IAAS 0.50% — 35.00% 100.00% 10.1 0.90% CFE-14 10.00%58.60% 5.00% — IA 0.50% — 25.00% 100.00% 10.1 0.90% CFE-15 10.00% 61.60%4.00% — IA 0.50% — 25.00% 100.00% 10.0 0.90% CFE-16 10.00% 46.15% 5.00%MSA IAAS 0.50% — 35.00% 100.00% 9.6 2.45% 0.90% HA = Hydroxylamine; PG =Propylene Glycol; MEA = Monoethanolamine; MSA = Methanesulfonic acid; IA= Isethionic acid; IAAS = Isethionic acid NH₄ salt; 5MBTA =5-methylbenzothiazole; DBU = 1,8-diazabicyclo[5.4.0]-7-undecene.

TABLE 2 Co W AlOx TiOx B-doped W Ex. (Å/min) (Å/min) (Å/min) (Å/min)(A/min) Cleaning FE-1 N/A N/A 3.90 N/A N/A Clean in 4 minutes FE-2 N/AN/A 2.90 N/A N/A Clean in 4 minutes FE-3 N/A N/A 1.60 N/A N/A Clean in3.5 minutes FE-4 0.6 4.2 1.0 0.4 60.3 Clean in 3.5 minutes FE-5 1.0 5.72.1 0.7 74.1 Clean in 3.5 minutes FE-6 0.7 4.8 1.8 0.5 68.5 85-90% CleanFE-7 0.7 4.6 1.2 0.5 70.0 Clean in 4 minutes FE-8 0.9 5.8 2.2 1.0 95.5Clean in 4 minutes FE-9 N/A N/A 1.5 N/A N/A Clean in 4 minutes FE-10 N/AN/A 1.7 N/A N/A Clean in 3.5 minutes FE-11 N/A N/A 2.4 N/A N/A Clean in3.5 minutes CFE-1 N/A N/A N/A N/A N/A Not clean in 6 minutes CFE-2 N/AN/A N/A N/A N/A Not clean in 6 minutes CFE-3 N/A N/A N/A N/A N/A Notclean in 6 minutes CFE-4 N/A N/A N/A N/A N/A Not clean in 6 minutesCFE-5 N/A N/A N/A N/A N/A Not clean in 6 minutes CFE-6 N/A N/A N/A N/AN/A Not clean in 6 minutes CFE-7 N/A N/A N/A N/A N/A 85-90% clean CFE-8N/A N/A N/A N/A N/A 85-90% clean CFE-9 N/A N/A N/A N/A N/A 85-90% cleanCFE-10 N/A N/A N/A N/A N/A 85-90% clean CFE-11 N/A N/A N/A N/A N/A85-90% clean CFE-12 N/A N/A 8.91 N/A N/A Clean in 4 minutes CFE-13 N/AN/A 1.86 N/A N/A Not clean in 6 minutes CFE-14 1.8 5.3 1.21  0.61 61.5Not clean in 6 minutes CFE-15 0.8 4.9 1.02  0.49 55.2 Not clean in 6minutes CFE-16 N/A N/A 1.52 N/A N/A Not clean in 6 minutes N/A = Notavailable.

As shown in Tables 1 and 2, formulations FE-1 to FE-11 (which containedappropriate amounts of monoethanolamine and isethionic acid or its salt)exhibited both excellent capability of cleaning post etch residues andcompatibility (i.e., relatively low etch rates) with semiconductormaterials (especially AlOx) that may be exposed in a cleaning process.By contrast, formulations CFE-1 to CFE-11 (which do not containmonoethanolamine) did not adequately clean post etch residues.Formulation CFE-12 contained a relatively high amount ofmonoethanolamine. Although formulation CFE-12 cleaned post etchresidues, it exhibited a relatively high AlOx etch rate (i.e., arelatively low compatibility with AlOx). Formulations CFE-13 and CFE-15contained a relatively low amount of monoethanolamine. The resultsshowed that, although these two formulations exhibited a relatively lowAlOx etch rate, they did not adequately clean post etch residues.Formulation CFE-14 contained a relatively low amount of DI water. Theresults showed that, although this formulation exhibited a relativelylow AlOx etch rate, it did not adequately clean post etch residues.

Other embodiments are within the scope of the following claims.

What is claimed is:
 1. A cleaning composition, comprising: 1)hydroxylamine in an amount of at most about 15% by weight of thecomposition; 2) an aminoalcohol comprising at least two amino groups andat least one hydroxyl group, the aminoalcohol being in an amount of atmost about 8% by weight of the composition; 3) hexylene glycol in anamount of at most about 50% by weight of the composition; and 4) water;wherein the pH of the composition is from about 8 to about
 11. 2. Thecomposition of claim 1, wherein the hydroxylamine is at least about 6%by weight of the composition.
 3. The composition of claim 1, wherein thehexylene glycol is at most about 30% by weight of the composition. 4.The composition of claim 1, wherein the water is at least about 20% byweight of the composition.
 5. The composition of claim 1, wherein thewater is at least about 40% by weight of the composition.
 6. Thecomposition of claim 1, wherein the water is at most about 50% by weightof the composition.
 7. The composition of claim 1, further comprising atleast one corrosion inhibitor.
 8. The composition of claim 7, whereinthe at least one corrosion inhibitor comprises benzotriazole optionallysubstituted by at least one substituent selected from the groupconsisting of alkyl groups, aryl groups, halogen groups, amino groups,nitro groups, alkoxy groups, and hydroxyl groups.
 9. The composition ofclaim 7, wherein the at least one corrosion inhibitor comprises acompound selected from the group consisting of benzotriazole,5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole,5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole,4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole,naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole,5-nitrobenzotriazole, 4-nitrobenzotriazole,3-amino-5-mercapto-1,2,4-triazole, 2-(5-amino-pentyl)-benzotriazole,1-amino-benzotriazole, 5-methylbenzotriazole, benzotriazole-5-carboxylicacid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole,4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole,5-isopropylbenzotriazole, 4-n-butylbenzotriazole,5-n-butylbenzotriazole, 4-isobutylbenzotriazole,5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole,4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-m ethoxybenzotriazole,5-hydroxybenzotriazole, dihydroxypropylbenzotriazole,1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-t-butylbenzotriazole, 5-(1′,1′-diimethylpropyl)-benzotriazole,5-(1′,1′,3′-trimethylbutyl)benzotriazole, 5-n-octyl benzotriazole, and5-(1′,1′,3′,3′-tetramethylbutyl)benzotriazole.
 10. The composition ofclaim 7, wherein the at least one corrosion inhibitor is from about 0.1%by weight to about 2% by weight of the composition.
 11. The compositionof claim 1, further comprising at least one pH adjusting agent, whereinthe at least one pH adjusting agent comprises an acid.
 12. Thecomposition of claim 11, wherein the at least one pH adjusting agent isfrom about 1% by weight to about 10% by weight of the composition. 13.The composition of claim 1, wherein the hydroxylamine is in an amount offrom about 6% by weight to about 15% by weight of the composition; thehexylene glycol is in an amount of at most about 30% by weight of thecomposition; and the water is at least about 20% by weight of thecomposition.
 14. The composition of claim 1, wherein the composition isfree of a metal halide.
 15. A method, comprising: contacting asemiconductor substrate containing post etch residues or post ashingresidues with a cleaning composition of claim
 1. 16. The method of claim15, wherein the semiconductor substrate further comprises at least onematerial selected from the group consisting of Cu, Co, W, AlOx, AlN,AlOxNy, Ti, TiN, Ta, TaN, TiOx, ZrOx, HfOx, and TaOx.
 17. The method ofclaim 15, further comprising rinsing the semiconductor substrate with arinse solvent after the contacting step.
 18. The method of claim 17,further comprising drying the semiconductor substrate after the rinsingstep.
 19. The method of claim 15, further comprising forming asemiconductor device from the semiconductor substrate.